Solvent Cage Effects and the Dynamics of Liquid State Chemical Reactions

点击翻译按钮获取中文摘要

In this project in the Theoretical and Computational Chemistry Subprogram of the Physical Chemistry Program, Adelman will study the dynamics of three elementary processes, vibrational energy relaxation, photolytic cage escape, and activated barrier crossing, which occur ubiquitously in liquid state chemistry. The goals of the proposed research are four-fold: (i) To obtain an improved understanding of the solute motions which underlie these elementary processes; (ii) To derive analytical formulas for observables like the vibrational energy relaxation time and the non-geminate quantum yield which transparently reflect the qualitative nature of the solute motions; (iii) To develop practical semi-quantitative prescriptions for choosing molecular solute friction kernels; and (iv) To develop simplified stochastic dynamics simulation methods for simulating the solute motions. This work should provide new fundamental understanding of liquid state reaction dynamics. It also should provide quantitative frameworks for the interpretation of experimental data. And lastly it should provide computational tools whose application will lead to further increases in knowledge.